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Combined modeling and experiments uncover the influence of epoxide-functionalization on hydrogen bonding and mobility within poly(ethylenimine) CO 2 sorbents, rationalizing the antidegradation benefits conferred by functionalization.
Bisphenol A-based epoxies are much used in a wide range of composite and coating applications due to their excellent thermomechanical properties. However, their 3D printability remains a challenge with most reported materials suffering from high brittleness and low toughness. In this work, we have described especially modified epoxy resins that enable 3D printing with both fast and slow curing rates. These materials exhibit greatly enhanced toughness, tunable thermomechanical properties, and excellent shape memory behavior. Two different printing systems, including a two-part static mixing printhead and a single extrusion printhead, were developed for fast- and slow-curing epoxies, respectively. The rheology of inks in both systems has been modified into printable thixotropic fluids with the aid of silica nanoparticles and other additives. Epoxide-functionalized telechelic polybutadiene was added into the resins, which are then introduced inside the epoxy network after cross-linking. The addition of polybutadiene rubber significantly improves the toughness (over 135%), fracture strain (over 200%), and shape memory behavior. By adding different amounts of the rubber telechelic, thermomechanical properties, including modulus, elongation, and Tg of epoxy, can be well controlled in a wide range to satisfy different applications.
Sulfuric acid under different concentrations and with the addition of SO 3 (fuming sulfuric acid) was studied as a reducing agent for the production of reduced graphene oxide (RGO). Three concentrations of sulfuric acid (1.5, 5, and 12 M), as well as 12 M with 30% SO 3 , were used. The reduction of graphene oxide increased with H 2 SO 4 concentration as observed by Fourier-transformed infrared spectroscopy and X-ray photoelectron spectroscopy. It was observed that GO lost primarily epoxide functional groups from 40.4 to 9.7% and obtaining 69.8% carbon when using 12 M H 2 SO 4 , without leaving sulfur doping. Additionally, the appearance of hexagonal domain structures observed in transmission electron microscopy and analyzed by selected area electron diffraction patterns confirmed the improvement in graphitization. Although the addition of SO 3 in H 2 SO 4 improved the GO reduction with 74% carbon, as measured by XPS, the use of SO 3 introduced sulfur doping of 1.3%. RGO produced with sulfuric acid was compared with a sample obtained via ultraviolet (UV) irradiation, a very common reduction route, by observing that the RGO produced with sulfuric acid had a higher C/O ratio than the material reduced by UV irradiation. This work showed that sulfuric acid can be used as a single-step reducing agent for RGO without sulfur contamination.
The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.
Ion-conducting polymers that are hybrids of organic and inorganic moieties and that are suitable for forming into solid-electrolyte membranes have been invented in an effort to improve upon the polymeric materials that have been used previously for such membranes. Examples of the prior materials include perfluorosulfonic acid-based formulations, polybenzimidazoles, sulfonated polyetherketone, sulfonated naphthalenic polyimides, and polyethylene oxide (PEO)-based formulations. Relative to the prior materials, the polymers of the present invention offer greater dimensional stability, greater ease of formation into mechanically resilient films, and acceptably high ionic conductivities over wider temperature ranges. Devices in which films made of these ion-conducting organic/inorganic polymers could be used include fuel cells, lithium batteries, chemical sensors, electrochemical capacitors, electrochromic windows and display devices, and analog memory devices. The synthesis of a polymer of this type (see Figure 1) starts with a reaction between an epoxide-functionalized alkoxysilane and a diamine. The product of this reaction is polymerized by hydrolysis and condensation of the alkoxysilane group, producing a molecular network that contains both organic and inorganic (silica) links. The silica in the network contributes to the ionic conductivity and to the desired thermal and mechanical properties. Examples of other diamines that have been used in the reaction sequence of Figure 1 are shown in Figure 2. One can use any of these diamines or any combination of them in proportions chosen to impart desired properties to the finished product. Alternatively or in addition, one could similarly vary the functionality of the alkoxysilane to obtain desired properties. The variety of available alkoxysilanes and diamines thus affords flexibility to optimize the organic/inorganic polymer for a given application.
Lignin-based syringol monomer, 2,6-dimethoxypropylphenol (DMPP), can be upgraded through two synthetic routes to multi-functional propylpyrogallol DMPPO and tri-epoxide which allows for various polymer applications.
Halohydrins are functional groups that are underexplored in polymer science. This study synthesized and examined structure–property relationships of halohydrin-functionalized polymers derived from polycyclooctene (PCOE), which was obtained via ring-opening metathesis polymerization (ROMP). The polyhalohydrins, including polychlorohydrin, polybromohydrin, and polyiodohydrin, were produced through a two-step process involving epoxidation of PCOE followed by epoxide ring-opening using hydrochloric, hydrobromic, or hydroiodic acid. These stereoirregular and regioirregular polymers are amorphous as measured by differential scanning calorimetry and X-ray scattering. Lap joint shear testing revealed an enhanced adhesive performance in polychlorohydrin and polybromohydrin, with the former demonstrating nearly three times the ultimate shear stress compared to a model polyethylene, hydrogenated PCOE. Additionally, contact angle measurements and surface free energy analysis showed an increase in hydrophilicity and polarity from iodine- to bromine- to chlorine-functionalized polyhalohydrins, aligning with trends in adhesion strength. Furthermore, these results underscore the potential of halohydrin functionalization as a versatile approach for tuning surface properties, offering new opportunities for polymer-to-polymer transformations.
Carbon nanotubes have attracted much interest in recent years due to their exceptional mechanical properties. Currently, the tensile properties of bulk carbon nanotube-based materials (yarns, sheets, etc.) fall far short of those of the individual nanotube elements. The premature failure in these materials under tensile load has been attributed to inter-tube sliding, which requires far less force than that needed to fracture individual nanotubes.1,2 In order for nanotube materials to achieve their full potential, methods are needed to restrict this tube-tube shear and increase inter-tube forces.Our group is examining covalent crosslinking between the nanotubes as a means to increase the tensile properties of carbon nanotube materials. We are working with multi-walled carbon nanotube (MWCNT) sheet and yarn materials obtained from commercial sources. Several routes to functionalize the nanotubes have been examined including nitrene, aryl diazonium, and epoxide chemistries. The functional nanotubes were crosslinked through small molecule or polymeric bridges. Additionally, electron beam irradiation induced crosslinking of the non-functional and functional nanotube materials was conducted. For example, a nanotube sheet material containing approximately 3.5 mol amine functional groups exhibited a tensile strength of 75 MPa and a tensile modulus of 1.16 GPa, compared to 49 MPa and 0.57 GPa, respectively, for the as-received material. Electron beam irradiation (2.2x 1017 ecm2) of the same amine-functional sheet material further increased the tensile strength to 120 MPa and the modulus to 2.61 GPa. This represents approximately a 150 increase in tensile strength and a 360 increase in tensile modulus over the as-received material with only a 25 increase in material mass. Once we have optimized the nanotube crosslinking methods, the performance of these materials in polymer matrix composites will be evaluated.
The toughness and coefficient of thermal expansion of a series of functionalized graphene sheet - epoxy nanocomposites are investigated. Functionalized graphene sheets are produced by splitting graphite oxide into single graphene sheets through a rapid thermal expansion process. These graphene sheets contain approx. 10% oxygen due to the presence of hydroxide, epoxide, and carboxyl functional groups which assist in chemical bond formation with the epoxy matrix. Intrinsic surface functionality is used to graft alkyl amine chains on the graphene sheets, and the addition of excess hardener insures covalent bonding between the epoxide matrix and graphene sheets. Considerable improvement in the epoxy dimensional stability is obtained. An increase in nanocomposite toughness is observed in some cases.
Traditionally, a catalyst functions by direct interaction with reactants. In a new noncontact catalytic system (NCCS), an intermediate produced by one catalytic reaction serves as an intermediary to enable an independent reaction to proceed. An example is the selective oxidation of ethylbenzene, which could not occur in the presence of either solubilized Au nanoclusters or cyclooctene, but proceeded readily when both were present simultaneously. The Au-initiated selective epoxidation of cyclooctene generated cyclooctenyl peroxy and oxy radicals that served as intermediaries to initiate the ethylbenzene oxidation. This combined system effectively extended the catalytic effect of Au. The reaction mechanism was supported by reaction kinetics and spin trap experiments. NCCS enables parallel reactions to proceed without the constraints of stoichiometric relationships, offering new degrees of freedom in industrial hydrocarbon co-oxidation processes.
Propylene oxide, a key commodity of the chemical industry for a wide range of consumer products, is synthesized through sequential propane dehydrogenation and epoxidation reactions. However, the lack of a direct catalytic route from propane to propylene oxide reduces efficiency and represents a major challenge for catalysis science. Herein, we report the discovery of a highly active and selective catalyst, made of alumina-supported subnanometer copper clusters, which can directly convert propane to propylene oxide at temperatures as low as 150 °C. Moreover, at higher temperatures, on the same catalysts, the selectivity is switched to propylene. Accompanying theoretical calculations indicate that partially oxidized and/or hydroxylated clusters have low activation energies for both propane dehydrogenation and propylene epoxidation pathways, enabling direct conversion with very high selectivity for propylene oxide. The discovery of a low-temperature catalyst that can convert propane directly to propylene oxide provides an important opportunity for the development of energy-efficient and economic catalysts for this industrially critical process. Similarly, when operating at higher temperatures, these catalysts are posed as potent oxidative dehydrogenation catalysts.
The exposure of most silicones to atomic oxygen in low Earth orbit (LEO) results in the oxidative loss of methyl groups with a gradual conversion to oxides of silicon. Typically there is surface shrinkage of oxidized silicone protective coatings which leads to cracking of the partially oxidized brittle surface. Such cracks widen and branch crack with continued atomic oxygen exposure ultimately allowing atomic oxygen to reach any hydrocarbon polymers under the silicone coating. A need exists for a paintable silicone coating that is free from such surface cracking and can be effectively used for protection of polymers and composites in LEO. A new type of silicone based protective coating holding such potential was evaluated for atomic oxygen durability in an RF atomic oxygen plasma exposure facility. The coating consisted of a UV curable inorganic/organic hybrid coating, known as a ceramer, which was fabricated using a methyl substituted polysiloxane binder and nanophase silicon-oxo-clusters derived from sol-gel precursors. The polysiloxane was functionalized with a cycloaliphatic epoxide in order to be cured at ambient temperature via a cationic UV induced curing mechanism. Alkoxy silane groups were also grafted onto the polysiloxane chain, through hydrosilation, in order to form a network with the incorporated silicon-oxo-clusters. The prepared polymer was characterized by H-1 and Si-29 NMR, FT-IR, and electrospray ionization mass spectroscopy. The paper will present the results of atomic oxygen protection ability of thin ceramer coatings on Kapton H as evaluated over a range of atomic oxygen fluence levels.
Parallel pathways for the postpolymerization modification of double bonds in a polycyclooctene (PCOE) backbone generate vicinal 1,2-diol-containing polymers with mixed but opposite stereochemistry, depending on the trans:cis ratio of the C═C in PCOE. Beginning from the same batch of PCOE, epoxidation and subsequent ring-opening with sulfuric acid and water produce a polymer with the majority erythro diols, whereas an osmium-catalyzed dihydroxylation results in diols in the majority threo orientations. These postpolymerization modification approaches enable access to previously unexplored polymers with a mixture of erythro and threo diols, offering tunable diol stereochemistry to tailor material properties. The majority erythro diols lead to hexagonal crystallites with higher melting temperatures and overall crystallinity when compared to the majority threo diols that form monoclinic crystallites. When blended, the two diastereomers phase separate as evidenced by distinct melting endotherms and crystal structures corresponding to the two component polymers, suggesting a route to tune the barrier or mechanical properties. Furthermore, this investigation synthesized polymers with mixed stereochemical diols and elucidated the thermal and morphological properties of regioregular linear poly(ethylene-co-vinyl alcohols) and their blends.
The synthesis of a linear poly-ethylenimine with pendant hydroxyl groups bonded to backbone carbons adjacent to the backbone amine groups is investigated and compared to the conventional method of functionalizing branched poly-ethylenimine using epoxides for use in direct air capture of carbon dioxide. The addition of hydroxyl groups imparts stability against both oxidative degradation and the formation of urea by reducing the number of primary amines, while the novel method of bonding to the adjacent backbone carbon rather than directly to the amine is hypothesized to retain the higher capacity for carbon dioxide of secondary amines when compared to tertiary amines. We also expect that the hydroxyl substituents will impart stronger hydrogen bonding capabilities, resulting in stronger interactions between adjacent polymer chains and a subsequent decrease in mobility.
Abstract Bio‐based photocurable polymers are increasingly in demand as environmentally friendly materials for advanced applications. Together with functional fillers, these represent a next step for the generation of functional and active smart materials, compatible with additive manufacturing technologies. Herein, acrylated epoxidized soybean oil (AESO) mixed with different amounts of reduced graphene oxide (rGO) up to 6 wt% in order to obtain UV‐curable piezoresistive and thermoresistive materials, is reported. It is shown that the addition of rGO to AESO hinders the curing process, but always maintains double bond conversions higher than 50%. Composites are characterized by a good dispersion of micrometric filler clusters. Further, the thermal stabilities are close to 300 °C and crosslinking degrees are above 1.75 mmol cm –3 . The Young modulus of the composites decreases with the addition of the rGO fillers, in particular for the higher filler contents, and electrical conductivities up to 0.13 S m –1 are obtained for the composites with the highest rGO content. UV‐curable composites with piezoresistive and thermoresistive responses suitable for applications are thus obtained, characterized by gauge factors around 26 for deformations up to 2% and maximum thermoresistive sensitivity of S = 0.43, values similar to the values obtained for petroleum‐based materials.
Compounds are useful as intermediates for several classes of polymers. Amines can function as cross-linking agents for epoxide and urethane polymers, as well as intermediates for synthesis of thermally-stable addition-type polyimides. Imide derivatives can be obtained by reacting amines with certain monoanhydrides containing olefinic unsaturation.
The reaction oxygen difluoride, OF2, with ethylenically unsaturated fluorocarbon compounds is examined. Depending upon the fluorocarbon material and reaction conditions, OF2 can chain extend fluoropolyenes, convert functional perfluorovinyl groups to acyl fluoride and/or epoxide groups, and act as a monomer for an addition type copolymerization with diolefins.
In this work we employed machine learning-augmented density functional theory (DFT) thermodynamic calculations to assess the stability of different AgO x structures under catalytic ethylene epoxidation reaction conditions. We found that there are multiple AgO x surface motifs that could co-exist under the relevant conditions. These included Ag surface oxides (e.g., AgO_p(4 × 4) and Ag 1.83 O) and atomic oxygen-covered Ag(111) surfaces. Furthermore, we employed DFT calculations to evaluate the energetics of different reaction mechanisms by which ethylene and oxygen can react on these surfaces. These studies revealed several energetically viable reaction pathways for ethylene epoxidation. Microkinetic modeling analyses, based on the DFT-calculated reaction pathways, showed that ethylene epoxidation can proceed on all surfaces and that multiple pathways, including those involving Langmuir–Hinshelwood and Eley–Rideal mechanisms, could be involved in selective and unselective reactions. The diversity of mechanisms that we discovered in the context of the relatively simple ethylene epoxidation reaction on Ag suggests that the richness and complexity of surface chemistry are most likely a rule rather than an exception in heterogeneous catalytic chemical transformations on metal surfaces and that the concept of a single or even a dominant mechanism and reaction intermediates might need to be revisited for many reactions.